Manufacture of side-chain aromatic



" July l 1941- L H. FLETT i, 2,247,365

MNUFACTURE 0F SIDE- CHAIN ARMATIC SLPHONATES Filed April 15. 1940 l700 60a' X INVENTOR y aw/'ence' /F/ef Patented July l, 1941 MANUFACTURE 0F SIDE-CHAIN AROMATIC SULPHONATES Lawrence H. Flett, Hamburg, N. Y., assigner to National Aniline & Chemical Company, Inc., New York, N. Y., a corporation of New York l Application April 15, 1940, serial No. szasso 16 claims.- (ci. 26o-505) The present invention relates to improvements in the manufacture of side-chain aromatic sulphonates which. are valuable detergents and wetting, emulsifying, and the like agents. One process lfor the'manufacture of these products involves chlorinating a hydrocarbon mixture of the type of a petroleum distillate. preferably a parailinic petroleum hydrocarbon distillate; condensing resulting chlorinated hydrocarbons with an aromatic compound with the aid. of a condensation catalyst of the Friedel-Crafts type,A

such as anhydrous aluminum chloride or anhydrous zinc chloride, to form a mixture containing aromatic compounds having nuclear side-chains; sulphonating resulting mixedr side-chain aromatic compounds; and recovering the resulting mixed sulphonic acids, preferably in the form of their salts. fsuch as their salts with alkali metals. T he inventionI particularly relates to improvements 'in the chlorination step of said process for the manufacture of the mixed side-chain aromatic sulphonates.

It is an object of the invention'to provide improvements in the step of the above process in which the hydrocarbon mixture of the type of a petroleum distillate is chlorinated, whereby mixed side-chain aromatic sulphonates possessing excellent properties may be obtained in highyields. A more specific object of the invention is to provide improvements in the chlorination step of the process of preparing mixed side-chain aromatic sulphonates involving chlorinating a. parafnic petroleum hydrocarbon distillate in which the hydrocarbons contain an average of 7 to 35 carbon atoms, condensing resulting chlorinated hydrocarbons with benzene, phenol, or naphthalene, sulphonating the resulting mixed vcondensation products, and recovering the mixed sulphonation product, preferably'in the form 'of an alkali metal salt; the improvement resulting in products of high quality which are obtained in excellent yields.

yOther objects of the invention will in part be obvious and will'in part appear hereinafter.

The mixed side-chain aromatic sulphonates with which the present invention is concerned are preferably derivatives of aromatic compounds of the benzene, naphthalene, and diphenyl series. T hus the products may be derivatives of benzene, naphthalene, diphenyl, or substituted members ofthe series to which these compounds belong, such as,V for example, compounds containing nuclear' substituents of which l halogens and hydroxyl, alkoxy, alkyl, and carboxyl radicals are examples. Where the aromatic compounds are substituted, they pref'ably contain but one substituent. As suitable substituted aromatic compounds there may be mentioned phenol, cresol, chlorbenzene, toluene, xylene, resorcinol, hydroxydiphenyl, phenetole, and benzoicacid. As pointed out above, the side chains present in the sulphonates'are derived from a hydrocarbon mixture of the type of a petroleum distillate; for example, a'kerosene or white oil` fraction' of petroleum, and preferably a parailinic petroleum hydrocarbon distillate. Thus the side chains are predominantly alkyl, cycloalkyL'or aralkyl radicals. Preferred products are composed predominantly of mono side-chain aromatic sulphonates in which the side=chains are alkyl radicals.

It is obvious that in order to produce superior products of the above type it is important to make certain that the side chains are of the desired character. It is also important, if the object is to prepare products adapted for general use, to obtain the mixed side-'chain aromatic sulphonates substantially free from the hydrocarbon mixture (e. g., the kerosene or white oil 'iractiom used in manufacturing the products.

In the manufacture of mixed side-chain aromatic sulphonates having the desired .type of side chains and therefore having desirable properties,

the manner. in which the chlorination of the hydrocarbon mixture is carried out is important. References in the literature disclose that when chlorinating a hydrocarbon mixture for the purpose of finally replacing a hydrogen atom of the hydrocarbon molecules with some other radical such as the hydroxyl group, the best yields of the desired products are obtained when at the end of the chlorination reaction, the amount of organically combined chlorine in the chlorinated hydrocarbon lmixture is much less than that which corresponds to one atom of chlorine per molecule of hydrocarbon. For example, Ayres l(Ind. Eng. Chem. 21, 899-904 (1929)) in discussing the chlorination of pentane for the purpose lof ypreparing amyl alcohol points out that one of the most important objects in the chlorination is the production of a minimum amount According to Ayres, the ideal method for preventing reaction of more than one molecule of chlorine with a pentane molecule would be to mix chlorine with an infinite excess of pentane and then allow reaction to take place.

lIn actual practice, Ayres was able to restrainl the formation of polychlorides very satisfactorily by using ratios of 20 parts of pentane to 1 part of chlorine. That chlorination ofthisnature,

which is conveniently termed underchlorination? should result in a high proportion of desired products from hydrocarbon'mixtures is also supported .by theoretical considerations. In

processes wherein a hydrocarbon mixture is-chlorinated so as to obtain from the mixture radicals of the hydrocarbon molecules. it has been considered that the useful products are obtained substantially entirely from the monochlorinated molecules. the polychlorinated molecules having been regarded as undesired impurities. t is known that the nrst chlorine atom intr uced into a hydrocarbon molecule at least does not seriously retard the introduction of further chlorine atoms into this molecule. For this Y reason, as chlorination is continued up to and beyond the point which corresponds to the introduction of one chlorine atom for each molecule ofhydrocarbons, it was to b'e expected that a larse Vproportion of the hydrocarbons present jhydrocarbons'in the mixture would be predomi- "nantly monochlorides, as the chlorination proceeded a proportion of these monochlorides would be converted into polychlorides. Although it would'be expected that continued chlorination would convert some of the unchlorinated hydrocarbons to the desired inonochlorides, it would be expected that this action .would be accompanied by the conversionof the monochlorides iirst formed into the undesired polychlorides, resulting in a final mixture containing a high proportion of the polychlorldes. 0n condensing the mixture containing the p'lychlorides with an aromatic compound, it would be t expected that the condensation taking place between the polychlorides and the aromatic compound would defeat the securing of desirable side-chain aromatic sulphonates upon the eventual sulphonation of the condensation products.

'Ihe present invention is based upon the discovery that the foregoing teachings and theoretical considerations do not hold true in the above-outlined general process for the manufacture of mixed side-chain aromatic sulphonates which are valuable for their detergent properties. 'I'hus it has been found that by chlorinating a hydrocarbon mixture of the type of a petroleum distillate, such as a kerosene or"white oi fraction of petroleum, and preferably aV paraiiinic petroleum hydrocarbon distillate, to such an extent that the amount of chlorine which has become combined organically in the mixture is more than that which would be so combined if each hydrocarbon molecule present in the mixture were converted to its corresponding monochloride, a chlorinated mixture is obtained which can be used successfully for the production of desirable mixed side-chain aromatic sulphonates with exceptional surface active properties. Hereinafter a chlorinated mixture containing vau amount of organically combined chlorine which exceeds that which would beA present if the mixture consisted of monochlorinated hydrocarbons only is said to be overchlorinated. It has further been found that by using an overchlorinated hydrocarbon mixture not only is it possible to obtain desirable mixed side-chain aromatic sulof hydrocarbon mixture employed, than when an underchlorinated hydrocarbon mixture is used.

A further advantage flowing from the over- 4chlorination procedure is that the desired mixed side-chain laromatic sulphonatescan be obtained more easily inV a form substantially free from unchlorinatedV By underchlorlnating a petroleum distillate, a chlorination product is which is composed to a large extent of unchlorlnated hydrocarbons'. Because of the similarity of the boiling points of the unchlorinated and chlorinated hydrocarbons in the mixture it is not feasible as a practical matter to separate them prior to condensation. After condensationit is dimcult to remove the unchlorinated hydrocarbons from the condensation products because'the'se hydrocarbons boil over a wide range which is not' suiiiciently diiferent from and usually overlaps the boiling range of the complex condensation products. By carrying out the chlorination of the hydrocarbon mixture to 'a degree greater than that corresponding to the introduction of one atom of chlorine for each atom of hydrocarbon (that is, greater than per cent chlorination on a molar basis), the unchlorinated hydrocarbons in the mixture are reduced to a minimum and may be removed by means not entirely successful when greater quantities of unchlorinated hydrocarbons arepresent.

There can be obtained at the present time special petroleum fractions which boil within relatively narrow ranges. However, such fractions are specialty products and are generally more expensive than the ordinary petroleum fractions which boilover wide ranges. The chlorination step of the present invention is particularly valuable, as compared with underchlorination, when used in a process for the manufacture of sidechain aromatic sulphonates from peroleum fractions tvhich boil over relatively wide ranges, such as kerosene fractions of petroleum. For example, in a case where a kerosene is used which boils over a range of 100 C. and the resulting' chlorination product is condensed with benzene, the individual compounds in the condensation product boil only about 40 C. higher than the individu al hydrocarbon compounds from which they were derived. Thus, some ofthe hydrocarbons in the unchlorinatcd hydrocarbon mixture have boiling points above the boiling points of some of the compounds in the condensation product. Consequently, separation of the unchlorinated hydrocarbons from the condensed products and from the side-chain aryl sulphonates which are made by sulphonating these condensed products is difficult. But where ,the4 proportion of unchlorinated hydrocarbons to condensed compounds is low, as where the present chlorination method is practiced, the dinlculties created by the presence of these unchlorinated hydrocarbons are greatly lessened.. Thus-when an overchlornated mixture of hydrocarbons is used for the condensation, the Yfraction of thel condensation product which contains the desirable side-chain aromatic compounds may be separated by distillation with lesser amounts of `unchlorinated hydrocarbons therein; furthermore.' when such a fraction is sulphonated, -the resulting side-chain aromatic sulphonate mixture retains less unsulphonatable hydrocarbons; andupon being subjected to a drying operation on adrum drier or in a spray drier, for example, someof these hydrocarbonsin the mixture are removed so that the amount of hyfac-raser;m

Y Y chain aryl sulphonate mixture is relativelysmall,

and its detrimental effects upon the washing action of the sulphonates are greatly lessened.v As statedabove, the chlorination of the hydrocarbonmixture in accordance with the present invention is carried out to a degree'such that the final chlorinated mixture contains more 'than one atom of organically combined chlorine for each hydrocarbonmolecule which was present in the mixture before chlorination. As a feature of the invention it' has been found that the yields of the `desired mixed side-chain aromaticY sulphonates generally increase with increase in the degree of chlorination until the hydrocarbon mixture contains an amount of organically combined chlorine corresponding to about one and one-half atoms of chlorine per molecule of hydrocarbon; that is,

the hydrocarbon mixture has been chlorinated to 20 tion of hydrocarbon mixtures the yields of the 'l desired side-chain aromatic sulphonates., based a degree which conveniently may be said to correspond to about "150 per cent chlorination.

Throughout this speciiication and the claims, per cent chlorination is on a molar basis; it refers to the per cent ratio between the actual increase in weight due to-chlorination of an "amount of hydrocarbon distillate corresponding to the average molecular weight ofthe hydrocarbons in the distillate and the expected increase in weight of the sameamount and kind of hydrocarbon dis- Y ,tillate if every hydrocarbon in the amount of hydrocarbon distillate were converted to its corresponding monochlor hydrocanbon. Thus, the

percent chlorination may 'be expressed by the` formula: (34.5+D) 100 where 34.5 represents thefincrease in weight of an average molar quantity of hydrocarbon mixturejif all the hydrocarbons in this quantity of mixture were converted to monochlor hydrocarbons only and (34.5-l-D) represents the actual increase in weight of an average molan quantity of hydrocarbon mixture due to 'chlorine' which is caused to become organically combineddn the hydrocarbons of the quantity of mixture by' the chlorination. Beyond the maximum point, which varies somewhat depending upon the specic hydrocarbon mixture treated and the conditions of chlorination, the yields of side-chain aromatic sulfonates derived from the resulting chlorinated hydrocarbon mixture begin to fall oi. It has vbeen determined that if chlorination of the hydrocarbon mixture is continued beyond-the point corresponding to 200 per cent of chlorination on a molar basis, the yields of derived side-chain aromatic sulphonates fall oi to such an extent as not to justify, from an economic standpoint, the use of the 'chlorine required. Accordingly, in accordance with the invention, the hydrocarbon mixture is chlorinated to a degree corresponding to more than 100 per cent, and not more than 200 per cent chlorination. Within these limits it is preferred to chlorinate the-hydrocarbon mixture to a degree corresponding to not more than 175 per cent chlorination. Especially valuable results are obtained when the chlorination is carried out to a degree corresponding to from 110 per cent to 150 per cent' tion of chlorine is kept at a reasonable level.

The chlorinationcan be carried out in any desired manipulative manner: for example, it

.chlorination may be effected by passing chlorine gas vinto abatch of the hydrocarbon mixture while agitating the batch or by contacting a stream of chlorine gas with a stream of the mixture. The extent of chlorination may be determined by th increase in, the speciiic gravity oi the hydrocarbon mixture chlorinated. The temperature at which the chlorination is effected may be varied over relatively wide limits. Al-

though thetemperature maintained has an effect upon the amount of side chain aromatic` sullphonates obtained from a given quantity ci* a hydrocarbon mixture, yet at all temperatures at whichV it is feasibleto carry out the chlorinaon the amount o f hydrocarbon mixture employed, are highest when the chlorination is carried out to a degree corresponding to more than 100 per cent and not more than 200 perecent chlorination.

It will be understood, of course, that the chlorination is ordinarily eected at the temperatures at which such operations are usually carried out;

rination may be carried out with the aid of chlorlne carriers, catalysts, or adluvants such as, for l example, phosphorus trichloride, iodine, sunlight, etc,

. e hydrocarbonmixtures employed in Vthe present process are complex mixtures, such as petroleum distillates, whose compositions are not definitely known. The-approximate composi- For the manufacture o products designed for general detergent use it is preferred to employ l petroleum fractions derived from Pennsylvania,

or Mount Pleasant, Michigan, petroleums which fractions boil for the most part within the range 180 to 300 C., and are preferably composed prewithin the range of 180 to" 280 C. Thus the preferred hydrocarbon mixtures are composed predominantly of saturated hydrocarbons, including saturated acyclic and saturated alicycl-ic hydrocarbons. containing an average fof 7 to 35 carbon atoms, or, better, 10 to' 19 carbon atoms, and especially 12 to 16 carbon atoms.

In order that the invntion may be understood more fully reference should be had to the following examples. For convenience, where a kerosene fraction of petroleum is used in the processes o disclosed in the-examples, the product obtained by chlorinating this fraction is termed keryl chloride and the product obtained by condensing the keryl chloride with benzene, for example,

tion of petroleum distillates is determined bydominantly of saturated hydrocarbons which'boil produc is termed "keryl benzene. It will be understood that the speciilc character of the keryl chlorld and keryl benzenes or other keryl aryl will be dependent upon the particular kerosene used and the manner in which the process is carried out.

Exmple l.-In order to demonstrate theadvantageous yields of keryl benzene sulphonates obtainable by means of the present invention, the following series of experiments was made:

At each of the temperatures 40 C., 60 C., 100 C., 120 C., and 140 C., a series o f chlorinated kerosenes was prepared. The chlorinated kerosenes in any series differed from each other in the extent of their chlorination. Each chlorinated lkerosene was condensed with benzene to form lkeryl benzene which was sulphonated by a procedure uniformly applied to each keryl benzene. It was found that at any temperature level of chlorination, the maximum yield of keryl benzene .sulphonates was obtained when the amount of organically combined chlorine in the chlorinated kerosene was between amounts required theoretically for complete monochlorination and dichlorination of all the hydrocarbons in the kerosene. This conclusion is supiorted by the data in Table 1 following. Details of the experimental procedure were as follows:

Part A.-0.2 gram iodine was dissolved in 500 grams of Pennsylvania kerosene having a boiling range of 185 to 275 C. While this kerosene,

containing iodine was vigorously agitated in a glass vessel and maintained at 40l 1 C., a stream of chlorine gas was conducted into it at the rate of about 2.5 grams per minuteuntil the desired degree of chlorination was reached. This was determined by blowing air through the chlorinated kerosene for a short time to remove dissolved chlorine and hydrogen chloride, and measuring the increase in weight of the kerosene caused by the organically combined chlorine therein.

Except for simple changes necessitated by the temperature at which the chlorination was made, the foregoing procedure was repeated with 500- gram portions of the same kerosene at temperature levels of 60 C., 100 C., 120 C., and. 140 C.

At 100 C., 120 C., and 140 C., chlorine gas was introduced into the kerosene through a ne glass capillary to obviate tendencies. towards ashing and soot-formation at the point of contact of chlorine gas and kerosene.

The chlorinated kerosenes prepared at 140 C. were not aerated, but were agitated for several minutes to remove dissolved chlorine and hydrogen chloride; it was observed that air passing through the chlorinated kerosene at about 140 C. impaired the quality of the preparation. The gain in weight by each of the several kerosene fractions due to their accession of organically combined chlorine ranged from about 20 per cent to about 200 per cent of the weight of chlorine which theoretically would have been combined in the kerosene fraction if it had been monochlof aumen which the mixture was agitated continuously. It was then transferred to avseparatory funnel and allowed to stand for about 16 hours. The lower tarry layer of the settled mass was drawn off and discarded. 'l'he upper layer of reaction product was fractionally distilled.

The excess benzene'present in the distilland was stripped by the distillatiomiirst at atmospherlc, and then at reduced pressure. The pressure' was then adjusted to 4 mm. of mercury andd a small fraction of distillate boiling up to was collected and discarded. The next fraction, containing the monokeryl benzenes, and consisting of all the material boiling between 80 and 250 C. under 4 mm.V of mercury, was then collected. A small amount of undistilled residue consisting largely ofpoly-phenylated kerosene benzene layer was then placed in a glass sulpho nating ask and agitated with 100 ccs. of-u100 per cent sulphuric acid which was run in during 1 0 minutes. 'Sulphonation of the keryl bnzene was completed by warming the mixture to 55 to 60 C. and maintaining the agitated mass at that 'temperature for about one hour. The'mixture was transferred to a separatory funnel and allowed to stratify for one hour; the middle layer of keryl benzene sulphonic acid was separated from the lower layer of spent sulphonating acid andthe top layer of unsulphonated hydrocarbon. 'I'he sulphonic acid layer -Was drowned in about 200 grams of ice, neutralized with 50 per cent aqueous caustic soda using additional ice as necessary to keep the temperature below 35 C. The neutral solutions 'were analyzed as follows: A 25 cc. aliquot portion of the neutralized solution was placed in'a tared beaker and evaporated to constant Weight at to 95 C., first at atmosfpheric pressure and then in vacuo in which the vacuum was gradually .increased to about 22 to 25 inches of mercury. From the weight of dry sample in the beaker, the total solids present in the solution were calculated. 'I'he sodium keryl benzene sulphonate content of the solids was determined by dissolving in 5 to l0 ccs. of water with gentle warming a one-gram sample of a drum-dried sample of the neutralized solution. To this solution, ccs. of anhydrous ethyl alcohol were then added; the alcoholic mixture was stirred thoroughly, then allowed to stand for 15 minutes, after which the precipitated inorganic salts were collected on a tared Gooch Crucible, washed with iivel 10 to 20 cc. portions of anhydrous alcohol, dried for' three hours at 100 C. and weighed. The difference between the weight of salt and weight of sample was the weight of keryl benzene sulphonate in the sample. Therefrom, the proportion of sodium keryl benzene sulphonate in the solids, and the amount of the former produced in the solution were then readily calculated. y

The eiect upon yield of sodium keryl aryl sulphonates, of variations in amount of organically combined chlorine in the chlorinated kerosenes from which they are derived, is seen in the'lollowing table:

Table! DegreeV rchlommion Yield expresse as (expreed. as Fergrams oi sodium T eentoichlorinat on) keryl benzene Sulempeftuf@ f assuming the nv, honteolltained l' tmofimmon M. W. of the keroilo oikerosenec orsenehydrocarbonsinatedv 189 y 27 71 47 154 7s 366 o Y g 520 40 C 119 620 13o 704 151 776 180 873 21 87 41 262 32 6l0 u 102 720 60 C 120 850 it at 199 870 23 m7 42 348 si 636 o 103 805 100 C 121 858 it si 41 386 63 516 83 670 u 104 829 120 C 125 924 144 990 170 y 985 192 990 45 384 32 626 103 740 122 ggg 139 140C 160 794 183 805 198 772 243 716 A continuous stream of Pennsylvania kerosene (boiling range 185 to 275 C.,speciiic gravity 0.792) was chlorinated `by contacting it with a stream of 'chlorine in a reaction zone and. continuously removing and cooling the chlorinated kerosene. The rate or kerosene ilow was varied from about 4 to about 12 ccs. per minute and the rate of chlorine flow about 5 to about 0.8 grams per minute. The temperature of the reaction in the reaction zone was about 130 C.

Depending on the amount of heat generated (which increased with the degree oi.' chlorination attained), the temperature in the reaction zone was controlled by preheating the kerosene 4or by passing cold air through an air jacket disposed about the chlorination apparatus to cool the re- -action zone. By varying the rate of flow o1 the chlorine and of the kerosene, portions of kerosene were chlorinated to varying degrees. 'I'he chlorination was carried-out in the absence of light.

The chlorinated kerosene samples so obtained were worked up into keryl benzene sulphonate by the methods described in Parts B and C of Example 1. 1

'I'he yields of sodium keryl benzene sulphonate. determined in the manner described in Example l, and obtained from the continuously chlorinated kerosene chloride samples are summarized in Table 2. Inworde'r to illustrate more clearly the eiIectof the degree of chlorination on the lyields of sodiumkerylbenzene sulphonate, the degree .i oi' chlorination (expressed as per cent oi'chlorination) was plotted against 'the yields of sodium kerylbenzene sulphonate. The resulting graph appears vin thedrawing, which is believed to be self-explanatory. vIt is pointed out that the products obtained-with the use of overchlorination were at -leastequal in quali-ty to those obtained using underchlorination. For example, the 724 grams of sodiumy keryl, benzene sulphonate obtained by chlorinating the kerosene to 117 vper' cent chlorination were at least equal in quality on a gram for gram basis to the 229 grams obtained bychlorinating the kerosene to 45 per cent chlorination.

As in Example 1, the results indicate clearly the advantageous etlect on yield of sodium keryl benzene sulphonates of chlorinating the kerosene portion toan extent between the chlorination corresponding to monoand di-chlorination of all the hydrocarbons in the kerosene portion.

Table 2 Yield expressed as Degree oi chlorination (expressed as pergrams oi sodium cent oi chlorination) assuming the averkeryl benzene sulage M. W. of the kerosene hydr0carbons= phonste obtained per 189 kilo of kerosene chlorinated Example 3.-A hydrogenated petroleum iraction which was derived from Louisiana crude oil and, to the extent of per cen-t, boiled between 200 and 355 C. at atmospheric pressure was fractionated under an absolute pressure of 4 mm. of mercury. The distillate boiling from to C. was collected. ,This cut of distillate had a specic gravity of 0i837 at 29 C. and had an average molecular weight of about 219. Each of two 219gram portions of this cut was chlorinated in a glass ilask exposed to diffused daylight. The chlorine was run in at a rate oi about 2.0 to 2.5 grams per minute. 'Ihe temperature of the chlorinating mixture during chlorination rose from 1'00111 'temperature to ar'ound 45 to 50 end of respectively, corresponding to a degree of chlorination of 84% and 113% chlorination.

Each batch of chlorinated kerosene was then condensed with an amount of phenol corresponding to one molecule oi' phenol per atom of combined chlorine in the batch. Thus, 80 grams and 106 grams of phenol were reacted with the hydrocarbon batches chlorinated to 84% and 113%. respectively. 15 grams of,anhydrous zinc chloride were used in each case as condensation catalysts. The condensation was carried outby agitating and heating the mixture of chlorinated` kerosene, phenol. and zinc chloride to around C. for about 7 hours. At` the end of this time, the reaction mixture was allowed to settle and the crude reaction product was poured oil.' the zincv chloride residues. The crude reaction product was then washed successively with 100 cc. portions of 10 per cent hydrochloric acid, hot water, and saturated aqueous sodium chloride solution. The washed crude product was then dried Awith anhydrous calcium chloride and distilled. 'Ihe desired keryl phenol product boiled between 140 C. and 220 C. at 5 mm. of mercury. The yields of desired products were 78 and 86 grams, respectively, for the batches of petroleum fraction chlorinated to 84% and 113%.

The two keryl phenol products were then separately sulphonated as follows: A -gram portion of thekeryl phenol preparation was placed in a glass flask, cooled torbelow 15 C., and 8.3 cc. of 100% sulphuric acid were run in. After agitating the mixture for one hour and allowing it to reach room temperature, the sulphonating mixture was warmed to 45 C. for one hour more, then it was poured onto about 200 grams of cracked ice and the aqueous mixture so obtained was neutralized with 50% caustic soda solution. The resulting solution was then drum dried.

On testing, it was found that the dried product made from the 113% chlorinated petroleum fraction was considerably superior to the dried product made from the 84% chlorinated batch. The superiority consisted in freedom from turbidity of the dilute solution of the product.

Example 4.-Commercial kerosene derived from Pennsylvania petroleum was fractionally distilled and the fraction boiling between 220 and 240 C. was collected. This fraction consisted of hydrocarbons which have a probable average carbon and hydrogen content corresponding to a formula: Cial-Ins to CraHza. A 199-gram portion was cooled to 0 C. and treated with a stream of dry chlorine in a glass flask fitted with a glass agitator. Introduction of chlorine was stopped when the weight of the chlorinated mixture had increased by about grams, of which 44 grams represented chlorine combined with the kerosene hydrocarbons. 'I'his degree of chlorination corresponded to about 115 per cent chlorination. The mixture was maintained at about 0 C. during the chlorination, which required about an hour and a half.

150 grams of this chlorinated kerosene were mixed with 65 grams of phenol and 50 grams of anhydrous zinc chloride. and the mixture was heated gradually. Voluminous amounts of hydrogen chloride gas were evolved at 60 to 110 C. On heating the mixture to 135 C., the evolution of hydrogen chloride abated; the mixture was then 'neld at 135 C. for one hour to complete the reaction. The oily portion of the reaction mass was decanted from the zinc chloride, and washed once with water to remove any zinc salts; it was then fractionally distilled under reduced pressure. The distillate, which boiled from 180 C. to 250 C. at 8 mm. was collected as product; yield was 53 grams of oil.

ccs. oi.' the keryl phenol distillate thus obtained were stirred, and thereto 35 ccs. of 100 per cent sulphuric acid were added slowly, the temperature of the mixture being kept at about 30 C. The sulphonation mixture was then warmed to 75 C. and held at that temperature (about 20 minutes) until a sample gave only a very slight precipitate of calcium salts from a calcium chloride solution containing the equivalent of 0.224 calcium oxide per liter. The sulphonation mixture was then diluted with water to about 500 parts by weight and neutralized with 50 per cent aqueous sodium hydroxide. The solution was evaporated to dryness on a drum drier. The ilnal product was a mixture of sodium salts of keryl phenol sulphonic acid o! the type:

R- SOaNa in which R represents the organic residue derived from the petroleum fraction which was chlorinated and condensed with phenol as previously described. Yield of product was 115 parts of dry naked material. 1

Example 5'.-10,620 lbs. of Pennsylvania kerosene (boiling range 185 to 275 C.) were charged into a lead-lined kettle fitted with lead-covered agitator, thermometer well and other accessories. 4.4 lbs. of iodine were dissolved in the agitated kerosene charge which was warmed to about C. and Vmaintained between 80 C. and 70 C. while chlorine gas was passed into the liquid at an average rate of about 300 lbs. per hour until the specific gravity of the chlorinated kerosene had changed from 0.788 at 24 C. before to 0.918 at 24 C. after the chlorination. The amount of chlorine required for the purpose was about 4,825 lbs. The final chlorinated kerosene mixture weighed about 12,834 lbs. The degree of chlorination corresponded to 114 per cent of chlorination.

A mixture of 13,272 lbs. of benzene and 332 lbs. anhydrous aluminum chloride was agitated and 6,636 lbs. of the foregoing chlorinated kerosene mixture were added thereto, over a period of 3 hours, during which the temperature of the mass rose to about 35 C. The mixture was then heated to 45 C. and held there for about an hour and a half. Agitation was then stopped and the kettle in which the liquid was stripped of low' boiling hydrocarbons, chietly benzene, by boiling the liquid at 150 C. ilrst under atmospheric pressure and finally under reduced pressure of 3 to 4 inches of mercury absolute pressure. The material left after this stripping was distilled in vacuo until about 7 per cent of the charge in the still had been removed as distillate. 'I'he remaining distilland was distilled, and distillate therefrom was collected separately until the boiling point of the distilland was 250 C. at 14 mm. mercury pressure. This last distillate was chiefly the condensation product of the chlorinated hydrocarbons of the kerosene fraction and the benzene; i. e., a keryl benzene.

The keryl benzene was Washed with per cent sulphuric acid by mixing it with about `15 per cent of its Weight of acid, and agitating the mixture in an enamel-lined kettle for about one hour at 30 to 35 C. The mixture was allowed to stand for about one-half hour to permit separation into layers. The spent sulphuric acid, which constituted the lower layer, was withdrawn and discarded.

The upper acid-washed layer of keryl benzene was mixed in an enamel-lined kettle with about 1.25 times its weight of 100 per cent sulphuric acid at a temperature between 30 and 35 C. The mixture was then warmed to 55 C. and agitated at that temperature for one hour. It was then allowed to stand for2 hours during which time three layers of material separated. The upper layer was chieily unsulphonated mateaaneen rial, the middle portion was chieiiy sulphonated keryl benzene, and the lower layer was spent sulj, phuric acid. The middle layer was separated absolute pressure of mm. of mercury more than 98 per cent distils overv the range 157 to 278 C. and more than 85 per cent distils over ther-ange., 195 to 260 C. For convenience, the

condensation products from white oil and benzene are called white-oil-benzene compounds.

2,270 lbs. of white oil were agitated in a vessel lined with lead. 1.75 lbs. of iodine were dissolved in the agitated white oil. Chlorine gas kwas then passed through the oil with continued agitation until the speciiic gravity of the sample showed an increase of 0.09 over that of the original white oil. During chlorination, the temperature was adjusted to 70 to 86 C. by suitably heating or cooling the batch. 'I'he chlorinated white oil weighed approximately 2,651 lbs. 'I'he degree of chlorination corresponded to about 150% chlorination.

, 617 lbs. of benzene and 62 lbs. of anhydrous aluminum chloride were agitated in an Allegheny metal kettle, warmed to 35 to 40 C. and held highly elcient detergent compositions for dry cleaning.

Example 7 .-A large batch of the kerosene used in Example 4 was rectiiled and the fraction boiling up to 91 C. under a pressure equal to 13 .mm. Vof mercury was collected. Approximately one gram f iodine was dissolved in 1000 grams of this kerosene fraction which was adjusted to a temperature of 50 to 55 C. and chlorinated directly, while it was agitated, with a `stream of chlorinegas. Chlorination was interruptedwhen the weight increase pf the chlorinated kerosene fraction indicated that it contained an at that temperature for about'an hour and a quarter during which period 617 lbs. of the chlorinated white 'oil (prepared as above-described) were run in. The agitated mixture was then warmed to 55 C. and agitated at .55 to 59 C. for an hour. The agitation was then stopped and the batch was allowed to settle for about 18 hours. During this period, the batch was allowed to cool down to about 30 C. Some 248 lbs. of tar which settled out were discarded.

The crude condensation product was transferred to a stripping kettle, and unrcacted benzene was stripped oi by gradually heating the batch to 150 C. and holding it at that temperature until distillation ceased and then simultaneously increasing the vacuum in the still to approximately 27 inches of mercury and gradually heating the distilland to about 175 C. The remaining stripped white-oil-benzene weighed 433 lbs.

200 lbs. of `4rstripped. white-oii-benzene were charged into an enamel-lined kettle tted with an enameled lagitator and other suitable accessories. The batch was then cooled to 16 C.

and 266 lbs. of 100 per cent sulphuric acid were 55 run in during an hour and a quarter. The tem-a perature was then raised to 50 to 55 C. and held there for about anl hour and a half.I 120 lbs. of water were then added slowly to the batch, which was cooled so that the ilnal and highest temperature thereof was 66y C. To the mix: ture, 80 lbs. of Stoddard solvent were added. After agitating the batch for 15 minutes, and then allowing it to stand for one hour, the lower spentacid layer was drawn oil. I'hen 80 lbs. more oi Stoddard solvent were added to the batch `which was agitated for 15 minutes and allowed to stand for about 18 Vhours before the rest of the spent acid was drawn off.

The sulphonation mixture was thenneutralized with 50 per cent aqueous caustic soda solution. The resulting product, which was a solution of white-oil-benzene-sodium-sulphonate in Stoddard solvent, is adapted for use in preparing amount of organically combined chlorine corresponding to 110 per cent of that'theoretically required for monochlorination of all the hydrocarbons in the kerosene. A mixture of 300 grams of this chlorinated kerosene, 180 grams of naphthalene, and 30 grams of anhydrous zinc chloride was agitated and heated .to 170 C. for- 16 hours. The condensation mixture was allowed to stand and settle; the olly layer was decanted from solid residue and distilled. The distillate boiling between 150 and 250 C. at 13 mm. o! mercury was collected as the desired keryl naphthalene.

20 grams of distilled keryl naphthalene were agitated for one-half hour at room temperature, with an equal volume of per cent sulphuric acid. The mixture was allowed to separate, and the lower, colored acid layer was withdrawn and discarded. The acid-washed kerylnaphthalene was sulphonated by agitating it with' 20 ccs. of per cent sulphuric acid for an hour and a half at 30 C. The sulphonation vmixture was drowned in about 300 ccs. of water, and neutralized with aqueous caustic soda solution, the temperature being kept below 40 C. 'during neutralization.' The neutral aqueous solution of sodium keryl naphthalene sulphonate was drum dried to obtain a dry composition which dissolved readily in water .to form substantially waterwhite solutions which had valuable detergent properties.

In the following examples, the parts are by weight:

Example 8,-A kerosene fraction of Pennsylvania petroleum distillate having a boiling range of about 172 to about 250 C., which, on the basis oi its source and properties, was consideredto be a mixture of hydrocarbons (mainlyuntil about 2l parts of chlorine had been absorbed per 100 parts of kerosene (corresponding to about 109 per cent chlorination). 200 parts of this mixture of chlorinated hydrocarbons were reacted at ordinary temperature with 150 parts of monochlorbenzene and 20 parts of anhydrous aluminum chloride. The temperature of the mixture was allowed to rise to about 60 C. with agitation and this agitation was continued for about one additional hour after this temperature was reached. The mixture was a1- lowed to stand and separate pinto two layersmi which the upper was decanted,'washed.with dilute hydrochloric acid and distilled until a vapor temperature of C. at 5 mm. was reached. The residue (85 parts) was an amber-colored oil comprising chiefly a mixture of alkyl chlorbenzenes in which the alkyl groups contained from about 10 to 15.5 carbon atoms. 20 parts of the oil were sulphonated by mixing it with 251/2` parte of 26 B. oleum at a temperature from about 10 to 15 C. for about 3 hours. The mixture was' then heated to 40 to 55 C., where it was held for about one-half hour. I'he mixture was then diluted by drowning it in 6 to 7 times its weight of ice and water, neutralized with concentrated aqueous caustic soda and dried. The resulting product was an almost white solid soluble in water to form substantially colorless solutions having desirable wetting and washing properties. The product was chiefly a mixture of nuclearly alkylated chlorbenzenes in which the alkyl groups contained from about 10 to about 15.5 carbon atoms.

Example 9, Part 1.-Chlorine was passed into a kerosene (a purified Pennsylvania petroleum distillate) which boiled from 245 to 315 C., and of which 90 per cent distilled between 260 and 305 C., and had a specic gravity of 0.815, contained in a closed, lead-lined vessel which was equipped with a vent for hydrogen chloride produced by the chlorination. I'he chlorination was carried out in the dark, but to vfacilitatefthe chlorination the kerosene initially contained about 0.45 part of iodine per 1000 parts of kerosene. The temperature of `the reaction mass was preferably maintained at about 45 to 50.** C. The introduction of chlorine was continued until the weight of the mass increased to an extent which corresponded substantially' with 115 per cent chlorination. The specic gravity of the reaction mixture reached about 0.915.

Part 2.-300 parts of the above chlorinated kerosene Was mixed with 30 parts of anhydrous aluminum chloride and 150 parts of commercial diphenyl. The mixture was agitated under reilux at room temperature (that is, at about 15 to 30 C.) for about one hour and thereafter at about 75 C. for about one and a half hours. The mass was then cooled to about 20 to 30 C. and poured into a mixture of 600 parts of ice water and 30 parts of commercial muriatic acid. 'Ihe aluminum salts dissolved in the cold dilute acid while the organic matter, which contained the alkylated diphenyl compounds, was precipitated in a semi-liquid, pasty form. Small amounts of benzene and/or ether were added to the agitated aqueous mix-ture to dissolve the organic products. Upon standing, the mixture separated into an upper layer which was a solution of the organic matter in the organic solvent, and a lower aqueous acid layer which was withdrawn and discarded. The benzoland/or ether solution of organic matter was washed with water until it was reasonablsr free of acid, and was then distilled in vacuo. The fractionof rthe distillate which boiled at labout 170 to about 260 C. atA 5 mm. pressure was collected separately. It was a. light-yellow viscous oil which was insoluble in water, but soluble in benzene and in ether. It was 'a mixture comprised chiefly of alkylated diphenyl compounds in which the alkyl groups corresponded with the kerosene' hydrocarbons employed. It also contained some chloralkyl diphenyl compounds derived from the dichlor hydrocarbons.

Part .3g-25 parts of theI oil obtained according to Part 2 of this example were mixed with 15 parts of 100 per cent sulphuric acid and stirred at about 90 C. for about 20 minutes, or until a 1 oc. sample was practically completely soluble in about 10 ccs. of Water at about 25 C. The sulphonation mass was poured into 300 parts of water and the aqueous acid mixture was neutralized with caustic alkali or a water-soluble carbonate (e. g., sodium carbonate), and the resulting neutral solution was dried. The product was chiey a mixture of the salts (e. g., alkali metal salts) of alkyl-diphenyl sulphonic acids. It was a light-brown to white solid winch was soluble in water, and in aqueous solutions of mineral acids and of water-soluble alkalies.

Example 10, Part 1.-Chlorine was passed into a kerosene (a purified Pennsylvania petroleum distillate) boiling from 245 to 315 C., and of which per cent distilled between 260 and 305 C., and had a speciic gravity of 0.815, contained in a closed, lead-lined vessel which was equipped with a vent for hydrogen chloride produced by the chlorination. 'Ihe chlorination was carried out in the dark, but to facilitate the chlorination the kerosene initially contained about 0.45 part of iodine per 1000 parts of kerosene. The temperature of the reaction mass was preferably maintained at about 45 to 50 C. 'I'he introduction of chlorine was continued until the weight of the mass increased to an extent corresponding substantially with per cent chlorination. The speciic gravity oi the reaction mixture reached about 0.915.

Part 2.-560 parts of the resulting mixture lol! chlorinated hydrocarbons, 350 parts of phenol and 28 parts of granular anhydrous zinc chloride were agitated at room temperature for about 3 hours and then heated, with agitation, at about C. for about 5 hours. The resulting reaction mass was cooled and added to about 600 parts 'of water, the ,mixture was heated to 70' C. with agitation, allowed to settle, and the upper,l oil layer was separated and washed with hot water to remove zinc chloride and residual phenol. The washed oil was then treated with a small amount of alkali (7 parts of a 50 per cent solution of sodium hydroxide) and distilled in vacuo (e. g., 4 mm. pressure) in a still equipped with a fractionating column. Fractions boiling between about and 230 C. at 4 mm. pressure were collected as separate products or as one product.

Part .3.-262 parts of one of the resulting mixtures oi' alkyl phenols (the resulting product or one of the fractions thereof) were sulphonated by agitating Well with 262 parts of 100 per cent sulphuric acid, while maintaining the temperature at 20 to 30 C. been effected'.' the reaction mass was drowned in 1500 parts of water, treated with sufficient caustic A soda to render it neutral to delta paper (about 260 partsv of a, 50 per cent solution of caustic soda) and evaporated to dryness.

It will be evident to those skilled in the art that the invention is not limited to the details of vthe foregoing illustrative examples and that changes can be made Without departing from the scope of the invention.

Thus, in using fthev chlorinated hydrocarbon mixtures prepared in accordance with the present invention the proportion of the aroma-tic compound employed may be varied. Generally, the'op'timum amount of aromatic compound to be employed is dependent upon the amount of chlorine combined in the hydrocarbon mixture. In order to obtain complete reaction, one mol of aromatic compound should be used for each atom When the sulphonation had tion i carried out forms no part of the present inven ion; this step can be carried out in any suitable manner. For example, sulphuric acids 'of various strengths such as 66 B, sulphurlc acid, 100 per cent sulphuric acid, 26 per cent.

oleum and 65 per cent oleum, and chlorsulphonic acid may be used as sulphonating agents. 'I'he sulphonation may be carried out in the presence of inert vsolvents or diluents, and sulphonation assistants as, for example, the lower fatty acids and their anhydrides, such. as acetic acid and acetic anhydride, orv the alkali metal sulphates, such as sodium or potassium sulphate, may be employed. Also, the temperature at which lthe sulphonation is carried out may vary Within wide limits.' For example, temperatures as lw as about 09 C. and as high as about 140 C. may be employed. In general. the more vigorous the sulphonating agent the lower is the preferred temperature. In most cases the sulphonation is carried out most eiciently at temperatures between v and 90 C. For complete sulphonation the sulphonating agent in terms of 100 per cent sulplruric acid may be employed in amounts which range from 0.3 to 5 times or more the Weight of 'the condensation product to be sulphonated. Ordinarily, the extent to which the sluphonation is carried outwill vary with the individual material being sulphonated, the duration of fthe sulphonation, and the use to .be made of the sulphonated product.

The side-chain aromatic sulphonates may be prepared in the formof their free sulphonic acids or in the form of their salts. Thus they may be prepared in the form of their alkali metal, alkaline earth metal, ammonium, or organic base salts (e. g., amine salts). 'I'hey are of particular value in the form of their alkali metal and especially sodium salts.

' This application is a continuation-in-part of my applications Serial No. 737,777, filed July 31,

1934; Serial No. 93,521, filed July 30, 1936; and Serial No. 186,231, led January 21, 1938.

' Since certain changes may be made in the process described above without departing from the scope of the invention it will be understood that the description should be interpreted as illustrative and not in a limiting sense.

I claim:

1. In the manufacture of side-chain aromatic sulphonates by chlorinating a hydrocarbon mixture of the type of a petroleum distillate, con- 'densing resulting chlorinated hydrocarbons with an aromatic compound, and sulphonating resulting side-chain aromatic compounds, the improvement which comprises chlorinating the hydrocarbon mixture to a degree corresponding to more than 100 per cent and'n'ot more than 200 vper cent chlorination.

2. In the manufacture of side-chain aromatic 'sulphonates by chlorinating ka hydrocarbon mixture of the type of a petroleum distillate containing an average of 7 to 35 carbon atoms, condensing resulting chlorinated hydrocarbons with an aromatic compound, and sulphonating resulting side-chain aromatic compounds, the improve- 4 ment which comprises chlorinating the hydrocarbon mixture to a degree corresponding to more than 100 per cent and not more than 175 per cent chlorination.

3. In the manufacture of side-chain aromatic sulphonates by chlorinating a hydrocarbon mixture of the type of a petroleum distillate containing an average of 7 to 35 carbon atoms, condensing resulting chlorinated hydrocarbons with an aromatic compound: Aand sulphonating resulting side-chain aromatic compounds, the improvement which comprises chlorinating the hydrocarbon mixture to a degree corresponding to from 110 to 150 per cent chlorination.

4. Inthe manufacture of side-chain aromatic sulphonates by chlorinating a. petroleum distillate containing an average of 10 to 19 carbon atoms permolecule, condensing resulting chlorinated hydrocarbons with an aromatic compound, and sulphonating resulting side-chain aromatic compounds, the improvement which comprises chlorinating the petroleum distillate to a degree corresponding to more than 100 per cent and not more than 175 per cent chlorination.

5. In the manufacture of side-chain aromatic sulphonates by chlorinating a hydrocarbon mix- 4ture of the type of a petroleum distillate containing. an average of 7 to 35 carbon atoms, con--` densing resulting chlorinated hydrocarbons with an aromatic compound of the benzene series, and sulphonating resulting side-chain aromatic compounds, the improvement which' comprises chlorinating the hydrocarbon mixture to a degree corresponding to more than 100 per cent and not more than 200 per cent chlorination.

6. In the manufacture of side-chain benzene sulphonates by chlorinating a. petroleum distillate containing an average of 7 to 35 carbonv atoms, "condensing resulting chlorinated hydrocarbons with phenol, and sulphonating resulting side-chain phenol compounds, the improvement which comprises chlorinating the petroleum distillate to a degree corresponding to more than per cent and not more than v200 per cent chlorination.

8. In the manufacture of side-chain naphthalene sulphonates by chlorinating a parailln'lc petroleum hydrocarbon distillate containing an average of 7 to 35l carbon atoms, condensing resulting chlorinated hydrocarbons with naphthalene, and sulphonating resulting side-chain naphthalene compounds, the improvement which comprises chlorinating the petroleum distillate to a degree corresponding to more than 100 per cent and not more than 200 per cent chlorination.

9. In the manufacture of side-chain aromatic sulphonates by chlorinating a parafllnic petroleum hydrocarbon distillate containing an averagevof 10 to 19 carbon atoms, condensing resulting chlorinated hydrocarbons with an aromatic compound, and sulphonat'ing resulting side-chain aromatic compounds, the improvement which comprises chlorinating the hydrocarbon mixture to a degree corresponding to from to 150 per cent chlorination.

10. In the manufacture of side-chain benzene sulphonates by chlorinating a parailinlc petrole-l um hydrocarbon distillate boiling for the most part Within the range to 300 C., condensing resulting chlorinated hydrocarbons with benzene, and sulphonating resulting side-chain benzene compounds, the improvement which comprises chlorinating the petroleum distillate to a degree not more than 175 per cent chlorination.

12. In the manufacture of side-chain benzene sulphonates by chlorinating a paramnic petroleum hydrocarbon distillate containing an average of to 19 carbon atoms, condensing resulting chlorinated hydrocarbons with benzene; and sulphonating resulting side-chain benzene compounds, the improvement which comprises chlorinating the petroleum distillate to a degree corresponding to from 110 to 150 per cent chlorination.

13. In-the manufacture of side-chain phenol sulphonates by` chlorinating a parailinic petroleum hydrocarbon distillate containing an average of 10 to 19 carbon atoms, condensing resulting chlorinated hydrocarbons with phenol, and sulphonating resulting side-chain phenol compounds, the improvement which comprises chlorlnating the petroleum distillate to a degree corresponding to from 110 to 150 per cent chlorinatlon. v

14. In the manufacture of side-chain benzene sulphonates by chlorinating a paralnic petroleum hydrocarbon distillate boiling for the most part within the range 180 to 300 C., condensing resulting chlorinated hydrocarbons with benzene inthe presence of anhydrous aluminum chloride, and sulphonating resulting side-chain benzene compounds, the improvement which comprises chlorinating the petroleum distillate to a degree corresponding to about per cent-chlorination.

15. The process for manufacturing side-chain aromatic sulphonates which comprises chlorinating a paraillnic petroleum hydrocarbon distillate containing anA average of 7 to 35 carbon atoms to a degree corresponding to more than 100 per cent and not more than 175 per cent chlorination, condensing the resulting chlorinated mixture with an aromatic compound with the aid of a Friedel-Crafts condensation catalyst to form a mixture of side-chain aromatic compounds, and sulphonating the mixture of sidechain aromatic compounds.

16. The process for manufacturing side-chain benzene sulphonates which comprises 'chlorinating a parafllnic petroleum hydrocarbon distillate Acontaining an average of 10 to 19 carbon atoms to a degree corresponding to more than 100 per cent? and not more than per cent chlorination, condensing the resulting chlorinated mixture with benzene with the aid of anhydrous aluminum chloride to form a mixture of sidechain benzene compounds, and sulphonating the mixture of side-chain benzene compounds.

LAWRENCE H. FLE'IT. 

